Process for preparing polyurethanes by interfacial polymerization



3,485,882 PRUCESS F PREPARING POLYURETHANES BY lNTERFA'QiAL POLYMERIZATION Wiliiam Kenneth Witsiepe, Wilmington, DeL, assignor to E. l. du Pont de Nemours and Company, Wilmington, Del, a corporation of Delaware No Drawing. Griginal application Dec. 30, 1963, Ser. No-

334,595, new latent No. 3,377,322. Divided and this application Mar. 7, 1968, Ser. No. 711,170

int. Cl. (108g 22/04 US. Cl. 25077.5 9 Claims ABSTRAQT OF THE DISCLOSURE Continuous process for the preparation of polyurethanes by interfacial polymerization of bishaloformates and organic diamines.

Priority This application is a divisional application of my copending application Ser. No. 334,595, filed Dec. 30, 1963, now US. Patent No. 3,377,322.

Background of the invention Injection and compression molding techniques are well known for the economical and rapid production of a variety of plastic items. These molding techniques are generally not applicable to the production of elastomeric parts because conventional elastomers are cross-linked and therefore are not thermoplastic; however, a few thermoplastic elastomers are known. These include the thermoplastic materials disclosed in U.S Patent No. 2,929,801 in which the polymer chain includes 10 to 40% by weight of high melting segments obtained by reaction between a diamine and halide of a difunctional acid, 60 to 90% by weight of polyether derived segments, and optionally a minor proportion of low molecular weight glycol derived segments. By following the teachings of this patent, particularly the disclosure of preferred combinations of diamine and difunctional acid, highly useful thermoplastic elastomers can be prepared by melt spinning or extrusion. Unfortunately, however, these polymers are not altogether satisfactory for processing by injection molding for the reason that such high molding temperatures are required that some chemical decomposition of the polyted States Patent 0 mer occurs. This is particularly the case under practical conditions encountered in commercial injection molding Where a relatively long exposure to high temperatures is required.

Another group of thermoplastic elastomers are the polyurethanes disclosed in U.S Patent No. 2,929,802. These contain 10 to 40% by weight of high melting segments obtained by reacting a diamine and a bishaloformate of a low molecular weight glycol, and optionally a minor proportion of diacid halide derived segments. While these elastomers possess very desirable properties and utility, they have the disadvantage of tending to be deficient in set properties when compared to conventional crosslinked elastomers.

Preparation of copolyurethanes such as those described in U.S.P. 2,292,802 and of the copolyurethane/amide copolymers described hereinafter has previously been effected by interfacial polymerization of bishaloformates and diamines in batch equipment or in constant composition continuous equipment such as disclosed in U.S.P. 2,658,886. Batch interfacial polymerization is an excellent procedure on a laboratory scale, but it is impractical as a means for producing copolyurethanes and related polymers on a commercial scale. On a large scale it is impossible to add and thoroughly mix the reactants as 3,485,802 Patented Dec. 23, 1969 quickly as may be done in the laboratory. Attempts to scale up batch polymerizations have yielded unacceptable products of relatively low molecular weight. Higher quality products can be obtained with the vigorously agitated constant composition continuous reactor of U.S Patent 2,658,886, but only if large excesses of the relatively expensive diamine component are employed. Thus the need exists for an economical commercial process for preparing high quality (high molecular weight) copolyurethanes by interfacial polymerization of bishaloformates and diamines.

Description of the invention The invention interfacial polymerization process produces thermoplastic elastomers which are especially suited for injection molding and which have desirable physical properties obtained when a few selected diamines are reacted with an amide-forming compound derived from certain dicarboxylic acids and with a bishaloformate of both a high molecular weight polyether glycol and a low molecular weight glycol, all in specific amounts. In particular, this improved characteristic is obtained when the diamine is piperazine or methyl substituted piperazine at the 2; 2,5; or 2,3,5,6 positions and the dicarboxylic acid is adipic or succinic acid. When other combinations of diamine and acid reactants are employed or the composition limits are not observed, as by the following disclosure of the above-mentioned patents, elastomers having the combined characteristics of injection moldability and adequate compression set are not obtained.

The thermoplastic elastomers produced according to the present invention can be defined as being linear or normally solid, and consisting essentially of the recurring units (a) -OGO, (b) OLO and (c) -D, all connected by the bivalent acyl radical wherein, OGO is a bivalent radical obtained by removing the hydroxyl hydrogen atoms from a polyether glycol having an average molecular weight of 800 to 3000; OL-O- is a bivalent radical obtained by removing the hydroxyl hydrogen atoms from a glycol having a molecular weight of less than 200; D is a linear C or C alkylene radical; and

is a bivalent acyl radical wherein Z is a bivalent radical obtained by removing the amine hydrogens from a diamine selected from the group consisting of piperazine, 2- methyl piperazine, 2,5-dimethyl piperazine and 2,3,5,6- tetramethylpiperazine, said recurring units (a), (b), and (c) being present in amounts of 40-60 parts, 5-25 parts, and 2-5 parts, respectively per parts of copolymer, all parts by weight, with the proviso that the elastomer contain units having the formula wherein the average value of n is greater than one. The improved conolymers of the present invention possess the unique combination of properties of being both injection moldable and having desirable elastomeric properties, particularly set.

The improved polyether/urethane/amide copolymers of the present invention are preferably prepared by reacting the bishaloformates,

and

and the diacid halide,

with at least a stoichiometric amount of a diamine, HZ-H, wherein G, L, D, and Z have the same meanings given above and X is selected from the group consisting of chlorine and bromine.

It has been found that copolyurethanes in general as well as the copolymers of this case can be conveniently prepared by a continuous interfacial polymerization process in which bishaloformates, an organic diamine and an acid acceptor are mixed in a low volume mixer and introduced into a pipeline having at least two inline mixers placed along its length. The pipeline should provide a hold up of at least about four minutes so that polymerization is substantially completed within the pipeline. The initial low volume mixer, the pipeline and the inline mixers should also be sized so that the ratio of the volume of the pipeline to the total volume of the initial and inline mixers is at least 15:1. This process provides an economical way to produce commercial quantities of copolyurethanes of high quality as indicated by their in herent viscosity.

The thermoplastic elastomers of the present invention, while completely soluble in many solvents, exhibit the usual characteristics of conventional reinforced, crosslinked elastomers. The polymers are probably linear as evidenced by their solubility behavior, but their properties suggest that they are reinforced by strong physical forces. In the present polyether/urethane/amide elastomers, these physical bonds can be ruptured reversably by heat at temperatures below those at which the polymer degrades chemically. On cooling to normal temperatures, the physical bonding is re-established and with it, the characteristics of conventional elastomers are re-established.

The following is a further descriptiomof the structural units constituting the improved copolymers of the present invention. All parts are by Weight.

The first structural unit, referred to as OGO, is a bivalent radical obtained by removing the hydroxyl hydrogen atoms from a polyether glycol, HOGOH, having a number average molecular weight of 800-3000. Polyalkyleneether glycols are the preferred polyether glycols for use in the present invention. They may be represented by the general formula HO(RO) H, wherein R is an alkylene radical which may be the same or different and n is an integer having a value such that the glycol has a number average molecular weight of 800- 3000. These glycols can be prepared by the polymerization of cyclic ethers such as alkylene oxides and tetrahydrofuran by known methods. Of the polyalkylene ether glycols, polytetramethyleneether glycol and polypropyleneether glycol are especially preferred. Other related glycols, such as polyalkyleneether-thioether glycols and polyalkylenearyleneether glycols may also be used. The strucural unit O-G-O', is preferably introduced into the copolymers of this invention by employing the glycol in the form of its bishaloformate.

The second structural unit, refer-red to as OL-O, is a bivalent radical obtained by removing the hydroxyl hydrogen atoms from a glycol, HOLOH having a molecular weight of less than 200. The glycols which may be employed to furnish this structural unit should contain two aliphatic hydroxyl groups. The bivalent radical L may be substituted with groups which do not interf re with. the pr paration or use of the copolymers,

Examples of such groups include alkyl, aryl, alkoxy, aryloxy, and alkenyl groups. Glycols in which the bivalent radical B is aliphatic, cycloaliphatic, or aliphaticaromatic may be used as long as both hydroxyl groups are connected to alphatic carbons. Specific examples of suitable glycols include ethylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5- pentanediol, 2-methyl-l,4-butanediol, 2-ethyl-2-methyl-l, 3-propanediol, 2-butyl 2 methyl 1,3 propanediol, 2-allyloxy methyl-Z-methyl-l,3-propanediol, cyclohexanediol and diethylene glycol. Mixtures of these glycols may be employed to advantage on occasion. Of these 1,4-butanediol and neopentyl glycol are especially preferred. A preferred mixture of glycols employs a 3:1 molar ratio of neopentyl glycol and butanediol-l,4. As in the case of the polyether glycol, the units derived from the low molecular weight glycol may be introduced into the polymers of this invention in the form of a bishaloformate.

The third structural unit, referred to as D, is a linear C or C alkylene radical which is the residue of and may be considered as derived from a dibasic acid HOOC-DCOOH. Suitable dibasic acids included are limited to succinic and adipic acids, with adipic acid being preferred. This structural unit, D, can, as indicated be introduced into the copolymers of this invention in the form of a diacid halide.

The fourth structural unit, referred to as is a bivalent acyl radical wherein Z is a bivalent radical obtained by removing the amine hydrogens from only certain diamines which are selected from the group consisting of piperazine, 2,5-dimethylpiperazine, Z-methyl piperazine, and 2,3,5,6-tetramethylpiperazine. These diamines are believed to be useful in the present invention because they have both a highly symmetrical ring and secondary amine groups. Of these diamines, piperazine is by far preferred because of tits availability. This structural unit may be introduced into the copolymers of the present invention by reacting a glycol bishaloformate or a diacid halide with piperazine or the named substituted piperazine.

The bivalent radical,

serves as the connecting link between the other polymer structural units; namely, OGO, OLO. and D. The units OGO- and O-L-O may occur in any order in the polymer chain as long as the D units, in combination with the connecting unit,

units. In other words, the combined units,

H II

-c-zomust be arranged so that the average value of n in the structures i i D Z which occur in the copolymer chains must be greater than one. The specialized urethane/amide copolymers of t p e t n enti n m st con a n the f ur yp s of s r ctural units in the amounts set forth. As a consequence, it is found that the polyether urethane/ amide copolymers have film-forming temperatures of less than about 225 C.

The film-forming temperature is a convenient measure of the suitability of polymers designed for use in compression and injection molding processes. This measurement was developed in connection with the work leading to the present invention. The film-forming temperature is determined in the following way. Approximately grams of freshly prepared polymer in granules about 3 mm. diameter is placed between two 6 x 6" pieces of heavy aluminum foil. This sandwich is placed between the heated platens of a hydraulic press and a pressure. of about 500 p.s.i. is applied with the platens heated to various set temperatures. The sample is held under heat and pressure for one minute. The lowest temperature which results in the production of a clear smooth-to-the-touch uniform film less than 0.25 mm. thick, which does not shrink appreciably on pressure release, is called the film-forming temperature. Film-forming temperatures are defined within :10 C. by this procedure. Copolymers of the present invention having film-forming temperatures in the range of about 150 C. to 255 C. have in general been found to be most useful and readily processible by compression and injection molding.

While the film-forming temperature gives an indication of the temperature requirements for injection molding, it is usually somewhat lower than the temperature actually required for commercial injection molding. Copolymers having film-forming temperatures below about 255 C. can be readily processed in commercial equipment at temperatures below and up to a limit of about 300 C. which represents the point at which decomposition begins to occur. Copolymers of the present invention having filmforming temperatures greater than only about 150 C. possess good elastomeric properties as indicated by conventional measurements of stress-strain, resilience, compression set, set at break, and tear strength. The elastomers of the present invention usually exhibit hardness in the Shore A 60 to 85 range. Copolymers having filmforming temperatures below about 150 C. generally are not as tough as those copolymers having higher filmforming temperatures; however, they are useful still in specialized applications and may be processed by injection or compression molding. In addition to predicting molding behavior, film-forming temperature is also an indication if a given copolymer will be soluble in selected solvents. In general, copolymers having film-forming temperatures below about 255 C. are completely soluble in suitable solvents and form gel-free solutions.

The polyether urethane/ amide copolymers of the present invention must contain between and 60 parts of -OGO units which are polyether derived units per 100 parts of copolymer in order to be processible and to have suitable elastomeric properties. If present in amounts of less than 40 parts per 100 parts of copolymer, the product tends to be more plastic in nature than elastic. If present in amounts of greater than 60 parts per 100 parts of copolymer, the product will lack toughness.

The units, D, which may be considered as being derived from a dicarboxylic acid, may be present in the copolymers of the present invention in amounts of 2 to 5 parts per 100 parts of copolymer. If greater than about 5 parts of these units are employed per 100 parts of copolymer, the resulting product usually has a film-forming temperature greater than 255 C. The minimum amount of these units which can be employed, that is, 2 parts, is required to produce a copolymer having adequate toughness. Copolymers containing from about 0.75 to 1.5 moles of -D units per mole of OGO units which also meet the composition requirements expressed in parts, represent a preferred class of polymers.

The structural units, OL--O, which are most conveniently derived from a low molecular weight glycol, can be present in the copolymers of the present invention in amounts of 5 to 25 parts per parts of copolymer. If the quantity of OLO units exceeds about 25 parts, the resulting product tends to be more plastic than elastic. Usually at least about 5 parts of these structural units per 100 parts of modified copolymer are required to produce a product having a film-forming temperature below 255 C. The exact amount of glycol required will vary with the particular lOW molecular weight glycol being employed and the film-forming temperature which is desired. In general, the lower the molecular weight of the O-L-O units, the smaller is the amount which is required to yield copolymer having an acceptable filmforming temperature. Thus, a given weight of ethylene glycol would be expected to give a product having a lower film-forming temperature than observed for a product containing the same weight of 1,4-butanediol. The structure of the particular glycol used also governs the amount of low molecular weight glycol derived units required. While it is dilficult to predict with certainty the effect of a specific low molecular weight glycol, it appears that symmetrical glycols in which the hydroxyl groups are not sterically hindered are generally required in greater amounts than unsymmetrical glycols in which the hydroxyl groups are sterically hindered. Compositions containing from 1 to 3 moles of the O-LO- units per mole of OGO units, which also meet the composition requirements expressed in parts by weight, represent a preferred class of copolymers.

The modified polyether urethane/amide copolymer elastomers of the present invention may be prepared most conveniently by what might be called a solution/interfacial polymerization. Briefly, this polymerization involves (1) partially reacting a mixture of polyether glycol bishaloformate, low molecular weight glycol bishaloformate and diacid halide, dissolved in an inert water-immiscible solvent, with piperazine or a substituted piperazine as previously named and (2) adding an aqueous solution of an acid acceptor such as sodium carbonate to neutralize halogen acid generated by the reaction of step (1) so that all of the piperazine is available to complete the reaction with the bishaloformates and diacid halide. This procedure may be employed for batch or continuous preparation of the subject elastomers. If carried out in the manner to be described hereinafter, it produces polymers of acceptable molecular weight in which the units,

are not isolated but are at least partially joined to one another so that the average value of n in o o D it Z t groupings is greater than one.

The required bishaloformates for use in this procedure may be either chloroor bromo-derivatives, but the bischloroformates are definitely preferred. The bischloroformates are conveniently prepared by adding polyether glycol, low molecular weight glycols or mixtures thereof to an excess of liquid phosgene and refluxing the resulting mixture for about 12 hours. Following the reaction, hydrogen chloride and excess phosgene are removed by passing a stream of dry nitrogen through the reaction mass. The bisbromoformates may be formed similarly from glycols and carbonyl bromide. Preparation of the diacid halides, which may also be either chloroor bromoderivatives, with chlorides preferred is well known.

The inert water-immiscible solvents which are used in the solution/interfacial polymerization should be capable of dissolving the polymeric reaction product. The solvent should not react at an appreciable rate with the reactants. In addition, it is usually desirable to use a low-boiling solvent to facilitate isolation of the poylmer. Many halogenerated aliphatic hydrocarbon solvents have been found to be useful for carrying out the polymerization. Halogenated hydrocarbons containing the group, CI-IX wherein X is bromide or chloride, are usually very good solvents and preferred examples include methylene chloride, chloroform, 1,1,2-trichloroethane and 1,l,2,2-tetrachloroethane. In carrying out the solution/interfacial polymerization the mixture of the three acid halide components is usually diluted to about concentration in the inert solvent selected. Piperazine or a substituted piperazine can be added as a solid, but preferably is added as a solution in the same solvent employed for the halide components. The concentration of the piperazine solution may have any convenient value but concentrations around 2% are preferred.

The aqueous solution of acid acceptor which is added after partial reaction between the halides and piperazine is required to react with hydrogen halide acid which is formed as a by-product during polymerization. The preferred acid acceptor is sodium carbonate which can be conveniently employed as a 10% aqueous solution. Other suitable acceptors include sodium hydroxide, sodium bicarbonate and potassium bicarbonate. An excess of piperazine may also be used at an acceptor, but the excess should be added as an aqueous solution. If a very large excess of piperazine is added directly to the mixture of halides in the inert solvent solution, the molecular weight of the product may be lowered. Tertiary amines, such as triethylamine and pyridine, may also be used as acid acceptors but should again be added in aqueous solution so that the latter stages of the reaction will occur under conditions of interfacial polymerization.

When the copolymers of the present invention are prepared by the solution/interfacial polymerization, piperazine or substituted piperazine may be conveniently employed in excesses of 1% and 10% of that calculated to be required for reaction with the mixture of the three acid halides. This excess is exclusive of any piperazine added as an acid acceptor. Because of the interfacial technique employed in the latter part of the polymerization, which apparently limits the availability of piperadine, an excess of piperazine does not lower the molecular weight of the polymer. However, if suflicient piperazine is not present, the molecular weight of the polymer will be low. Rather than attempt to add the exact amount of piperazine required and run the risk of being short on piperazine, it is usually preferred to deliberately add a limited excess.

The solution/interfacial polymerization can be performed batchwise by preparing a solution in a suitable solvent of the two bishaloformates and the diacid halide in a vessel equipped for vigorous shearing agitation, such as a Waring Blendor. To this solution is added piperazine or substituted piperazine either as a solid or a solution. This addition may be started at room temperature and should be performed as rapidly a possible without causing the reaction mass to boil over. Within about 3060 seconds after the addition of the piperazine is started, 10% aqueous sodium carbonate is added as rapidly as possible. Since the reaction is exothermic, the temperature will rise but will not exceed the boiling point of the solvent as long as solvent may evaporate. Control of the temperature without the loss of excessive amounts of solvent vapor can be easily accomplished by adding ice. Once all of the ingredients have been added, the reaction is usually complete within about 4 to 20 minutes. The addition of the solution of sodium carbonate must be completed rapidly once started for if only a part of solution is added some of the piperazine will not be available and remaining acid halides will start to react with water which was introduced along with the sodium carbonate. Thi hydrolysis is undesirable ecause it introduces more or less monofunctionally into the polymer. The diacid halide, the most reactive material of the three halide components, appears to be most susceptible to this hydrolysis.

Following the reaction, the copolymer may be isolated by steam distilling away the solvent, filtering and washing to remove salts. Vigorous agitation is desirable during solvent removal since the copolymer will separate in small particles under these conditions rather than in large masses which may be formed with poor agitation. The isolated polymer may be dried in an air or vacuum oven.

In performing the polymerization batchwise, one is not restricted to the order of additions described above. For example, piperazine or substituted piperazine, acid acceptor, water and the inert organic solvent may all be placed in the agitated reaction vessel to which is then rapidly added a mixture of the three acid halide components. This scheme of addition apparently is satisfactory because the acid halide components are extracted and dissolved into the inert organic phase present in the reactor before they have a chance to hydrolyze with water phase. It is also possible to run the polymerization by adding an aqueous solution of acid acceptor and piperazine to a solvent solution of the three halide components contained in a reactor. Addition of any one of the three acid halide components without mixing with the other two components is undesirable because the units derived from the three halide components should be distributed more or less randomly along the polymer chain, with the exception of course, that a portion or the units derived from the diacid halide should be joined in groups of more than one. In the solution/interfacial polymerization, the joining of some of the acid halide derived units in groups of more than one unit appears to be accomplished automatically when all three types or halides are present as a mixture because the reactivity of the diacid halide is much greater, perhaps 1000 times greater, than the reactivity of the bischloroformates and the quantity of piperazine actually available at any given time throughout the course of the reaction is less than the stoichiometric requirement.

Preparation of the copolymers, according to the present invention, also may be performed by continuous solution/interfacial polymerization. Equipment for such continuous preparation can consist of two well-agitated vessels in series. A solution of the three acid halide components and piperazine solution are continuously introduced near the bottom of the first vessel. Partially reacted mass is removed from the top of this vessel by overflow and contacted with acid acceptor in the second vessel. Obviously, the streams are fed to the reactors at rates such that all ingredients will be present in the proper amounts and at a total rate such that the holdup times in the vessels will permit the reaction to approach completion. This system, while exceedingly simple, has a serious drawback. In order to produce satisfactory polymer with it, a relatively large excess of piperazine must be employed, for if only the stoichiometric equivalent of the three acid halides is employed the contents of the second reactor will be running at zero or close to zero piperazine concentration at all times. As indicated under the discussion of batch solution/interfacial polymerization, operation in the absence of piperazine or in the presence of only a trace of piperazine permits hydrolysis of the acid halide components and especially the hydrolysis of the diacid halide. The net result is the introduction of monofunctionality into the polymer which lowers the molecular Weight of the product.

The need for employing large excesses of piperazine, which is uneconomical even if excess material is recovered, can be avoided by employing different equipment in the continuous solution/interfacial polymerization. in the preferred types of equipment, back-mixing is minimized after the reactants have been brought together.

One convenient form of apparatus which minimizes backmixing consists of a long pipeline giving a hold-up time of at least about 4 minutes with about three low volume mixers placed along the pipeline to insure proper contacting of the system. The first mixer should be placed in the pipeline near the point at which the solutions of acid halide mixture and piperazine are introduced. Better still, the solutions may be introduced directly into the mixer. Following the first mixer, an aqueous solution of acid acceptor is added. Subsequent mixers are required because the system after the addition of acid acceptor tends to separate into two layers until considerable polymerization has taken place. After some polymerization has occurred, the polymer present serves as a surface active agent and permits a relatively stable emulsion to be formed. Once a stable emulsion has been produced, further mixing is not required for the completion of the reaction. Operating in this fashion simulates the batch procedure in which the acid halides and piperazine are quickly brought together and shortly thereafter, the acid acceptor is added rapidly. Other forms of reactors in which back-mixing is minimized may also be used. For example, one may use a number of vigorously agitated reactors (connected in series) with the acid halide and piperazine feeds being introduced into the first reactor and the overflow from the first reactor passing through the second and so on. Using this system, acid acceptor is introduced into one of the reactors following the first reactor. A much elongated reactor or a reactor compartmented with screens with agitation in each stage may also be used with feeds being added at suitable positions. Isolation of the polymer following continuous preparation may be performed batchwise or continuously. Recovery of the polymer which separates after steam distillation of solvent can be accomplished by either batch filtration and washing or by continuous filters capable of continuous washing.

Many of the compounding agents used in conventional elastomers may be employed to advantage in the copolymers of the present invention. Actually, it is desirable to employ antioxidants in the present elastomers. Useful antioxidants include such materials as 2,2-methylenebisi-methyl 6 tertiary-butylphenol), symmetrical di-B- naphthalamine-p-phenylene diamine and nicket dibutyldithiocarbamate. These materials are effective in preventing oxidative degradation when employed at levels ranging from about /2% to 2% by weight. They may be added to the copolymer of the present invention by dry mixing. However, it is preferred to add the antioxidants to the polymer slurry resulting from steam distillation, prior to isolation and air drying. When this is done, the polymer is protected against oxidation even during the latter stages of isolation.

The polyether urethane/amide copolymers of this invention have many uses. As previously indicated, they are ideal for compression or injection molding and thus may be used for a variety of accurately molded elastomeric parts. They are especially suited for molding complex mechanical forms such as gears, gaskets, belts and seals. In addition, articles can be formed from the polymers by blow molding, transfer molding and vacuum forming techniques. Extruded goods may be made from the copolymers in the form of rods, films, sheets, tubing, gasketing and nets. The elastomers may be calendered onto fabrics and other similar substrates. Fibers or filaments having outstanding properties may also be produced from these materials by means of melt spinning. The elastomers may be used as hot melt adhesives. Because of their adhesive properties and thermoplastic behavior, the copolymers of the present invention may be used as bonding or laminating agents in preparing safety glass.

The following examples will better illustrate the nature of the present invention. However, the invention is not intended to be limited to these examples. Parts are by weight unless otherwise indicated.

EXAMPLE 1 A mixture of 500 grams of polytetramethyleneether glycol (number average molecular Weight about 1000) and grams of 1,4-butanediol is added to 1 liter of liquefied phosgene contained in a 2-liter flask. This mixture is refluxed for 12 hours. The temperature of the mass during this step is about 9 C. Excess phosgene is removed from the reaction product by heating to 25 C. and passing dry nitrogen through the mass which is agitated vigorously. This treatment is continued until the content of phosgene is reduced to below ppm. (The concentration of phosgene in the bischloroformate is determined by titration with a solution of triethylarnine in benzene. In this titration, one mole of phosgene is equivalent to one mole of triethylamine. The end point is determined potentiometrically.) About 770 grams of mixed bischloroformate is obtained.

About 250 grams of the mixture of bischloroformates produced above and 29.3 grams of adipyl chloride are added to 2250 ml. of methylene chloride contained in a l-gallon Waring Blendor. The Blendor is turned on and 57.8 grams of anhydrous piperazine is added in about 30 seconds. Agitation is continued for one minute after which 800 ml. of sodium carbonate solution, prepared using 10 grams of sodium carbonate per 100 ml. of Water is added. Agitation is continued for an additional 20 minutes and 2.8 grams of 2,2'-methylenebis(4-methyl-6- tertiary-butylphenol) is added and blended in. About 1 liter of water, is added to the Blendor and steam is passed through the mass to remove methylene chloride. Agitation is continued in the Blendor during this latter operation and the polymer precipitates in the form of fine particles as the solvent is removed. Polymer is collected on a filter and is washed with hot Water until the sulfated ash content of the polymer on a dry basis is reduced to 0.1 to 0.2% by weight. The washed copolymer is dried in an air oven at a temperature of about C. for 5 hours. The approximate water content of the dry polymer is 0.5%.

The quantities of reactants used in preparing this copolymer correspond to 1 mole of polytetramethyleneether glycol, 2 moles of 1,4-butanediol, 1 mole of adipyl chloride, and 4.2 moles of piperazine. Piperazine is employed in excess and only about 4 moles are incorporated into the polymer. The composition corresponds to 55.7, 9.9, and 3.1 parts per 100 parts of copolymer of polyether, loW molecular weight glycol and diacid units, respectively.

The film-forming temperature of this polymer is about 225 C., measured by the procedure described in the disclosure. The film-forming temperature of the corresponding polyether/ amide copolymer is 300 C. Test pieces for stress-strain measurements and compression set measurements are prepared by molding in a 1- ounce Watson-Stillman injection molding machine operated at 250 C. and 7500 p.s.i. with a 30 C. mold temperature without indication of any degradation by heat. Stress-strain test pieces and compression set pellets are also prepared by compression molding at 225 C. and about 100 ps.i. for 1 minute and cooling the mold before releasing the pressure. Properties of both compression and injection molded copolymer, prepared by the procedure given above, are as follows:

Injection Compression Disc Tear, p.l 228 Yerzley Resilience, 25 0., percent 80 Compression Set, percent (22 hrs. at 70 C.) 59 Hardness, Shore A 80 M300, T p.s.i 6100 E percent 660 S percent 209 The stress-strain properties of this material are comparable to those of the piperazine copolymer, but set at break is nearly double that of the piperazine copolymer.

EXAMPLE 2 A mixture of bischloroformates is prepared by reacting 500 grams of polytetramethyleneether glycol (number 12 EXAMPLE 3 This example illustrates the changes in properties for a series of copolymers containing the same molar amount of low molecular weight glycol derived units and increasing amounts of diacid derived units. The property changes observed With 2 sets of compositions are presented.

The 5 copolymers of the first series each contain 1 moles of low molecular weight glycol derived units originating from Z-ethyl-Z-methylpropanediol-1,3 for each mole of polytetramethyleneether glycol derived units. The required mixture of bischloroformates is prepared by adding 47.2 grams of Z-ethyl-Z-methylpropanediol-1.3 and 200 grams of polyeteramethyleneether glycol (molecular weight about 1000) to about 750 ml. of liquid phosgene and proceeding as in Example 1. The amounts or reagents employed in preparing the copolymers, their compositions in parts per 100 parts, and physical properties are presented in Table I. Copolymer A which contains no diacid derived units was prepared by the same procedure used for copolymers BE.

TABLE I.EFFECT OF ADIPIC ACID UNITS ON THE PROPERTIES OF A COPOLYTIRE- THANE PREPARED FROM 2 MOLES OF Q-ETHYL-Z-METHYLPROPANEDIOL-L3 AND MOLE OF POLYTETRAMETHYLENEETHER GLYCOL (1000) Copolyrner Sample A B C D 1 Moles of diacid units /mole of polyetlier glycol units 0. 0 0. 5 1.0 1. 5 1 Mixed biscliloroformates, g 50.0 2:). 0 50. 0 25. l) 1 Reagents:

Adipyl chloride, g 1 1. 42 5. 67 4. 26 v 1.5 Piperazine, g 8. 38 4. 88 11. 18 5. 68 v 12 Copolymer composition in parts/100 parts:

Diacid units 1. 1. 6 3. 0 4. 3 l. Polyetlier units 60. 5 57. 1 54. 1 51. 4 as Low M.W. glycol units 14. 0 13. 3 12. 5 11. U .1. Copolymer physical properties:

2. 62 2. 41 2. 3. l6 490 800 890 1 1'00 4, 200 5, 900 6, 300 h s00 EB, percent 890 730 750 160 SB, percent 21 19 19 i l Tear strength, D-470, p.l.i 44 78 17 Film forming temperature, C 200 220 I60 1 Weak gum.

average molecular Weight about 1000) and 104 grams of neopentyl glycol with phosgene following the procedure given in Example 1.

A portion of the mixed bischloroformates is converted to polymer by the procedure given in Example 1, but at /s the scale used in Example 1. About 50 grams of mixed bischloroformate, 5.78 grams of adipyl chloride and 11.42 grams of anhydrous piperazine are employed.

Other reagents are employed in /5 the amount used in Example 1. Preparation is carried out in'a l-quart Waring-Blendor. The polymer so produced contains the equivalent of 1 mole of polytetramethyleneether glycol, 2 moles of neopentyl glycol, 1 mole of adipyl chloride and 4.0 moles of piperazine. Its composition corresponds to 54.9, 11.2 and 3.1 parts per 100 parts of copolymer of polyether, low molecular weight glycol and diacid units, respectively.

The film-forming temperature of this polymer is about 200 C. The polymer may be injection molded at 250- to 275 C. and 7500 p.s.i. in a 30 C. mold. Test pieces prepared by compression molding at 225 C. and 1000 p.s.i. for 1 minute have the following physical properties:

M300, T p.s.i 6700 E percent 590 S percent 0 Disc tear, p.l.i 89 Yerzley resilience, 25 C., percent 77 Compression set, percent (22 hrs. at 70 C.) 32 Hardness, Shore A 68 The polymer is soluble in a 1:1 methylene chloride 1,1,2-trichloroethane solvent mixture.

The four copolymers of the second series contain two moles of low molecular weight glycol units derived from neopentyl glycol for each mole of polytetramethyleneether glycol derived units from glycol having a number average molecular Weight of about 1000. The required mixture of bischloroformates for preparing these. copolymers is obtained by adding 104 grams of neopentyl glycol and 500 grams of polytetramethyleneether glycol to about 1 liter of liquefied phosgene and proceeding as in Example 1. Weights of reagents, polymer composition and physical properties are presented in Table II. Copolymer F was prepared from the mixture of bischloroformates. without adding adipyl chloride, by the same procedure used for homopolymers G4.

The data in the two tables indicate that an increase in the amount of diacid derived units in the presence of a constant amount of low molecular weight glycol derived units increases the film-forming temperature and yields tougher copolymers. Copolymers A and F contain no diacid derived units; copolymer A is a weak gum and copolymer F is a deficient in properties when compared with similar copolymers containing diacid derived units. With the maximum amounts of diacid units employed in preparing these copolymer series, the film-forming temperature is raised to a level too high to permit commercial injection molding. Copolymers containing 0.5 to 1.5 moles of diacid derived units and low molecular weight glycol units as indicated have outstanding elastomeric properties and film-forming temperatures which permit commercial injection molding.

EXAMPLE 4 This example illustrates the continuous preparation of polyurethanes according to this invention. The preparation is carried out in a pipeline reactor which employs centrifugal pumps spaced at intervals along the pipeline mixture containing 63.7% polytetramethyleneether glycol bischloroformate, 25.9% neopentyl glycol bischlorofor- Copoly'rner Sample F G H I Moles of diacid units/mole of polyether glycol units 0.0 1. 1. 2. 0 Mixed bischloroformates, g 50. 0 50.0 50. 0 50. 0 Reagents:

Adipyl chloride, g 5. 78 8, 67 11. 56 C Piperazine, g t t [100 t 8. 55 11. 42 12. 85 14. 29

o olymer composi ion in par 5 par s:

Diacid units. 3. 1 4. 4 5. 6 Polyether units 61. 6 54. 9 52. 1 49. 6 Low M.W. glycpl units.t 12. 6 11. 2 10. 6 10. 1 Co 01 er h sica r0 er ies:

Mggfi p L p p 1, 150 1, 140 1, 625 2, 200 TB, p.s.i 4, 700 6, 700 8, 100 7, 400 EB, percent 580 590 525 560 SB, percent. 15 0 25 Tear strength, disc, p.l.i 88 89 150 175 Yerz. resilience, 25 0., percent- 85 77 67 64 Compression set, percent 22 hrs 50 32 32 28 Hardness, Shore A 82 65: 7 5 80 Film-Forming temperature, C... 160 22a 240 275 as mixers. In order that the pumps may serve more efliciently as mixers, they are installed so that they pump against the fiow of process materials through the pipeline. Feed streams to the pipeline reactor are supplied at a sufiiciently great pressure to overcome the back pressure created by the centrifugal pumps. About 1049 grams per minute of a solution of 19 grams of piperazine in 1030 grams of methylene chloride is introduced into a short length of 0.62-inch ID pipe which is connected to the outlete of a centrifugal pump (pump cavity 50 ml.; rotor speed, 2400 rpm) About 87.5 grams per minute of a mixture containing 64.8% polytetramethyleneether glycol bischloroformate (prepared from glycol having a molecular weight of about 1000), 24.7% butanediol-1,4 bischloroformate and 10.5% adipyl chloride is introduced into the pump cavity through an inlet in the side of the pump casing. The two streams are well mixed by the centrifugal pump and the resulting blend of materials passed through about 2 feet of 0.62-inch ID pipe after which 330 ml. per minute of aqueous sodium carbonate is introduced' The carbonate solution is introduced just before the stream from the first pump mixer enters the outlet port of a second centrifugal pump similar to that previously described. Temperature in the pipeline between the first and second pumps and prior to the addition of sodium carbonate solution is in the range of 5055 C. Following the second pump, the reaction mass passes through 10 feet of 0.62-inch ID pipe, a third pump mixer, an additional 10 feet of 0.62-inch ID pipe, a fourth pump mixer and finally through 30 feet of additional 0.62-inch ID ipe. Throughout these latter portions of the system, the temperature of the reaction mass ranges from 40-50" C. After passing through the last length of pipe, the reaction mass discharges from the pipeline through a letdown valve set at p.s.i.g. The ratio of the reactor volume provided by the pipeline to the total volume of the mixers is about 15:1 in this example. About 0.9 gram per minute of 4,4'-butylidene-bis (6-tertiary-butyl metacresol), in the form of a solution of methylene chloride, is added to the reaction mass issuing from the pipeline. The reaction mass discharges into the vessel having a holdup of about 18 liters where the reaction is completed.

Methylene chloride is removed from the product mass by steam distillation. Copolymer is collected by filtration and washed with hot water. After drying in air at 120 C. for five hours, copolymer is formed into stress-strain test pieces and compression set pellets by compression molding. The polymer has essentially the same properties as the copolymer prepared batchwise in Example 1.

The copolymer prepared batchwise in Example 2 can also be made continuously following the procedure described above by feeding about 89 grams per minute of mate and 10.4% adipyl chloride in place of the 87.5 grams per minute of mixed bischloroformates and adipyl chloride used above.

What is claimed is:

1. A process for preparing polyurethanes by continuous interfacial polymerization wherein (1) a water-immiscible, inert organic solvent solution of bishaloformate is initially intimately mixed with at least an equivalent of an organic diamine followed by (2) intimately mixing the mixture resulting from (1) with an aqueous solution of an acid acceptor and (3) maintaining the mixture of (2) as a mixture for at least about four minutes total bold-up time by passing said mixture through a pipeline having at least two inline mixers, where the ratio of the total volume in the pipeline to the volume in the mixers is at least about 15:1.

2. A method for preparing polyurethanes by continuous interfacial polymerization wherein (1) a water-immiscible, inert organic solvent solution of bishaloformate, (2) at least an equivalent of an organic diamine and (3) an aqueous solution of an acid acceptor are intimately mixed, the resulting initial mixed efiluent being fed continuously into a pipeline providing a hold-up of at least about four minutes, wherein polyurethane formation is substantially completed, said pipeline having at least two inline mixers, with the proviso that the ratio of the volume provided by said pipeline to the total volume provided by said mixers is at least about 15:1.

3. The method of claim 1 wherein said organic diamine is piperazine.

4. The method of claim 1 wherein said organic diamine is a piperazine substituted with methyl at the 2-, 2,5-, or 2,3,5,6-positions.

5. The method of claim 1 wherein said bishaloformate comprises substantially a mixture of one mole of the bischloroformate of a polyalkyleneether glycol having a molecular weight of at least about 1000, and at least one mole of the bischloroformate of a glycol having a molecular weight of less than 200.

6. The method of claim 1 wherein the acid acceptor is sodium carbonate.

7. The method of claim 5 wherein said polyalkyleneether glycol is a polytetramethyleneether glycol and said glycol having a molecular weight of less than 200 is butanediol-1,4.

8. A process for preparing polyurethanes by continuous interfacial polymerization wherein (l) a water-immiscible, inert organic solvent solution of bishaloformate and a diacid halide in an amount sufficient to supply 2 to 5 parts of alkylene radicals per parts of copolymer is initially intimately mixed with at least an equivalent of an organic diamine followed by (2) intimately mixing the mixture resulting from (1) with an aqueous solution of an acid acceptor and (3) passing said mixture of (2) through a pipeline having at least two in-line mixers Where the pipe line provides a total hold up time of at least four minutes and the ratio of the volume of the pipeline to the total volume of the mixers is at least 15 to 1.

9. The method of claim 8 wherein the bishaloformate is a mixture of one mole of the bischloroformate of a polyalkyleneether glycol having a molecular weight of at least 1000 and at least one mole of the bischloroformate of a glycol having a molecular Weight of less than 200, the diacid halide is adipyl chloride, the diamine is piperazine and the acid acceptor is sodium carbonate.

References Cited UNITED STATES PATENTS 2,658,886 11/1953 Swerdlotf et a1. 260- 77. 5 2,929,801 3/1960 Koller 26077. 2,929,802 3/1960 Katz 26077. 3,022,334 2/1962 Frazer 26077.5 K

DONALD E. CZAJA, Primary Examiner 10 M. J. WELSH, Assistant Examiner US. Cl. X.R. 

